Amongst various polymers, the biocompatible and biodegradable elastomer, poly(glycerol-sebacate) (PGS) has shown great promise in soft tissue scaffolding. PGS can be easily synthesized from glycerol and sebacic acid. Biocompatibility studies of PGS have shown excellent compatibility with a wide range of cells and tissues both in vitro and in vivo. However, PGS processability into nano-/microfibers still remains problematic. Fibrous scaffolds are considered advantageous for tissue engineering due to at least their extracellular matrix (ECM) mimicking properties, high surface area to volume ratio and anisotropic mechanical properties. The contact guidance provided by these fibers can be used to regulate cell orientation and migration. Fibrous scaffolds also have improved mechanical strength and suture retention compared to other scaffold structures, making them advantageous for surgical implantation. Thus, the ability to fabricate PGS fibers may be beneficial for tissue engineering applications by simultaneously providing contact guidance and superior mechanical properties. However, pure PGS is naturally difficult to electrospin. As stated by Yi et al. (Macromol. Biosci. 8(9): 803-806, 2008), “despite repeated efforts it was not possible to directly electrospin (and cure) nanofibers from either the polymerized PGS or the PGS prepolymer.” There is no solvent for cross-linked PGS and PGS pre-polymer cannot form electrospun fibers on its own because it has a low molecular weight which precludes sufficient polymer chain entanglement to form fibers. PGS pre-polymer is also a viscous liquid at room temperature, causing any fibers formed to fuse rapidly after formation. Thus, there is a need in the art to develop methods of electrospinning PGS which allow stable PGS fibers and fibrous PGS scaffolds to be formed.